Thermal deamination kinetics of the nickel-containing chabazite-like aluminophosphate, Ni(NH2-CH2-CH2-NH2)2(AlPO4)6(OH)2, deposition of nanocrystalline NiO particles

Thermogravimetrical analysis has been used to study the kinetics of thermal deamination of bis(ethylenediamine)nickel(II)-containing aluminophosphate (Ni-CHA) which is a precursor of nickel(II)-containing chabazite-like AlPO₄-34. The deamination occurs as a single-step kinetic process which is best described by the contracting cylinder model. The obtained activation energy of 200 kJ/mol is mainly a reflection of the strong Ni-N coordination bond. The thermal decomposition of Ni-CHA results in the deposition of crystalline NiO particles homogeneously dispersed in the AlPO₄-34 lattice. Average particle size was found to be about 5 nm. The study confirms that the thermal decomposition of amine complexes of Ni(II) encapsulated inside the microporous aluminophosphate host can be a suitable method for obtaining fine nano-oxide particles.     

Synthesis and crystal structure of the MgCl2(CH3COOC2H5)2· (CH3COOC2H5) adduct

The reaction of α-MgCl₂ with boiling ethyl acetate affords MgCI₂(CH₃COOC₂H₅)₂· (CH₃COOC₂H₅), which is obtained as crystals suitable for X-ray analysis only from the mother liquor. M=315.5, orthorhombic, space group P2₁22₁ (No. 18), a=25.077(3), b=8.616(1), c=7.345(1) Å, V=1587.0(3) ų, Z=4, D_x=1.32 g cm⁻³,λ A(Mo Kα)=0.71069 Å, μ=4.17 cm⁻¹, F(000)=664, T=298 K, observed reflections: 1667, R=0.059 and R_w=0.069. The structure is composed of polymeric chains of MgCl₂(CH₃COOC₂H₅₎₂ and the ethyl acetate molecules occupy a mutually trans position.     

Syntheses, characterizations and crystal structures of two lead(II) diphosphonates: Pb2[NH(CH2PO3)2] · 2H2O and Pb3[HO2C(CH2)3NH(CH2PO3)2]2 · 2H2O

Hydrothermal reactions of lead(II) acetate and HO₂C(CH₂)₃N(CH₂PO₃H₂)₂ at 170 and 140 °C, respectively, resulted in two different lead diphosphonates, namely, Pb₂[NH(CH₂PO₃)₂] · 2H₂O (1), in which the butyric acid moiety of the HO₂C(CH₂)₃N(CH₂PO₃H₂)₂ has been cleaved and a novel layered compound, Pb₃[HO₂C(CH₂)₃NH(CH₂PO₃)₂]₂ · 2H₂O (2). Their crystal structures have been determined by single crystal X-ray diffraction. In compound 1, the interconnection of the lead(II) ions by bridging amino-diphosphonate ligands leads to the formation of a 3D network. Compound 2 features an unusual triple-layer structure with the non-coordinated butyric acid moieties as pendant groups between the layers.     

Spectroscopic and electrochemical properties of a new nitrosyl-complex of Ru(II): trans-[Ru(NO){(CH3CH2)2PCH2CH2P(CH2CH3)2}2Cl](PF6)2

A new ruthenium nitric oxide complex with the bidentate phosphine, 1,2-bis(diethylphosphino)ethane (depe), has been synthesized and characterized by UV-Vis, infrared, EPR, NMR, electrochemical techniques and X-ray structure determination. The electronic spectrum showed a typical band of dπ→pπ* charge-transfer (CT) transition, assigned to Ru(II)NO transition, and the vibrational spectrum exhibited a peak of nitrosyl ligand at (ν_NO=1851 cm⁻¹). A model structure for this complex has been proposed based on ¹H, ¹H{³¹P}, ³¹P{¹H}, ¹³C{¹H}, COSY ¹H¹H{³¹P}, J-Resolved, HSQC, HMBC, HSQC ¹H¹³C{³¹P} and ¹H¹³C HSQC/¹H¹H TOCSY spectral data, and confirmed by X-ray diffraction. The nitrosonium character for the NO ligand become evident through both electron paramagnetic resonance and X-ray data (angle RuNO=177.4(3)°). The reversible monoeletronic process at E_1/2=0.040 V versus SHE was assigned to the ligand NO⁺/NO redox couple. Under treatment with Cd(Hg) solutions containing the [Ru(NO)(depe)₂Cl](PF₆)₂ yields a signal in the EPR spectrum (g_⊥=1.99 and g_//=1.88) which fitted quite well with the simulated spectra of coordinated NO species.     

Structure and thermal behavior of the layered zincophosphate [NH3-CH2-CH(NH3)-CH3](ZnPO4)2

A zinc phosphate with the composition [NH₃-CH₂-CH(NH₃)-CH₃](ZnPO₄)₂, containing the doubly protonated 1,2-diaminopropane (abbr. HDAP), was synthesized by hydrothermal crystallization of zinc nitrate, phosphoric acid, 1,2-diaminopropane and trimethylenedipiperidine. The single crystal analysis shows a layered inorganic-organic structure built up of a sandwich-like motif of alternating inorganic layers and HDAP cations (trimethylenedipiperidine not being a constituent of the structure). The HDAP species are found to be disordered and serve as bridges between two adjacent inorganic layers which are separated by 3.95 Å. The bridging interaction occurs via a hydrogen-bonding network. The inorganic layer features a pattern of four-membered rings involving two ZnO₄ and two PO₄ tetrahedra connected by sharing O atoms. Thermal analysis shows that the compound is stable up to 370 °C and that the thermal decomposition of HDAP occurs in two steps between 370 and 460 °C, causing the collapse of the structure. The first decomposition step corresponds to ammonia removal which proceeds with a high activation energy (E_a = 282 kJ mol⁻¹). The high E_a value is mainly attributed to strong electrostatic interactions between organic cations and anionic inorganic layers, the disruption of the interactions being the main reason for structural collapse after the HDAP removal.     

Synthesis and characterization of complexes of the type [Pt(amine)4]I2 and trans-[Pt(CH3NH2)2(H3CNC(CH3)2)2]I2 by crystallography and multinuclear magnetic resonance spectroscopy

Complexes of the type [Pt(amine)₄]I₂ were synthesized and characterized mainly by multinuclear (¹⁹⁵Pt, ¹H and ¹³C) magnetic resonance spectroscopy. The compounds were prepared with different primary amines, but not with bulky amines, due to steric hindrance. In ¹⁹⁵Pt NMR, the signals were observed between −2715 and −2769 ppm in D₂O. The coupling constant ³J(¹⁹⁵Pt-¹H) for the MeNH₂ complex is 42 Hz. In ¹³C NMR, the average values of the coupling constants ²J(¹⁹⁵Pt-¹³C) and ³J(¹⁹⁵Pt-¹³C) are 18 and 30 Hz, respectively. The crystal structure of [Pt(EtNH₂)₄]I₂ was determined by X-ray diffraction methods. The Pt atom is located on an inversion center. The structure is stabilized by H-bonding between the amines and the iodide ions. The compound with n-BuNH₂ was found by crystallographic methods to be [Pt(n-BuNH₂)₄]₂I₃(n-BuNHCOO). The crystal contains two independent [Pt(CH₃NH₂)₄]²⁺ cations, three iodide ions and a carbamate ion formed from the reaction of butylamine with CO₂ from the air. When the compound [Pt(CH₃NH₂)₄]I₂ was dissolved in acetone, crystals identified as trans-[Pt(CH₃NH₂)₂(H₃CNC(CH₃)₂)₂]I₂ were isolated and characterized by crystallographic methods. Two trans bonded MeNH₂ ligands had reacted with acetone to produce the two N-bonded Schiff base Pt(II) compound.     

植物排放N2O和CH4的研究

N₂O和CH₄是2种重要的温室气体, 但其排放源尚未得到充分鉴别。1990年和2006年先后报道植物能排放N₂O和CH₄, 并日益受到广泛的关注。然而, 迄今为止对植物排放这2种气体的研究均是分开单独进行的。该文以8种陆生草本植物为研究对象, 首次同步考察了新鲜离体植物地上部排放N₂O和CH₄的通量。研究结果表明: 8种植物均能排放这2种气体。其中, 黑麦草(Lolium perenne)、抱茎苦荬菜(Ixeridium sonchifolium)和菠菜(Spinacia oleracea)的CH₄通量较高, 分别为165.38、 52.28和21.64 ngCH₄·g^–1dw·h^–1; 抱茎苦荬菜、蒙古蒿(Artemisia mongolica)、大豆(Glycine max)和菠菜的N₂O通量较高, 分别为7.19、6.92、5.44和4.05 ngN₂O·g^–1dw·h^–1。研究结果不仅为植物本身既能排放N₂O又能排放CH₄在植物中可能具有普遍性提供了进一步的实验依据, 而且为深入研究其机理找到了几种适宜的植物种(如抱茎苦荬菜、菠菜)。     

A seven-coordinate Fe compound: [Fe{O(CH2CO2)2}(H2O)2(NO3)]. Preparation, structure and magnetic properties

A seven-coordinate Fe^III complex, [Fe(oda)(H₂O)₂(NO₃)], was obtained after dissolving Fe(NO₃)₃ · 9H₂O in an aqueous solution of oxydiacetic acid (H₂oda) at room temperature. In the solid state, the Fe^III center adopts a pentagonal bipyramid geometry with an {FeO₇} core formed by a tridentate oda²⁻ and a bidentate in the equatorial plane, and two axial water molecules. Magnetic measurements and EPR spectra revealed the presence of S = 5/2 Fe^III centers with rhombic zero field splitting parameters (D = 0.81 cm⁻¹, E/D = 0.33 ). Weak antiferromagnetic interactions with J ≈ −0.06 cm⁻¹ operating between neighboring Fe ions connected through Fe-O-C-O?H-O-Fe paths are estimated using the molecular field approximation.     

Solution-mediated syntheses and characterizations of two new zincophosphites [C6H14N2]0.5[Zn(H2PO3)2] and [C4H12N2]0.5[(CH3)2NH2][Zn2(HPO3)3]

Two new zincophosphites [C₆H₁₄N₂]_0.5[Zn(H₂PO₃)₂] 1 and [C₄H₁₂N₂]_0.5[(CH₃)₂NH₂][Zn₂(HPO₃)₃] 2 have been solvothermally synthesized in mixed solvents of N,N-dimethylformamide (DMF) and 1,4-dioxane (DOA), respectively. Single-crystal X-ray diffraction analysis reveals that compound 1 exhibits a neutral inorganic chain formed by ZnO₄ and HPO₂(OH) units. Interestingly, the left- and right-handed hydrogen-bonded helical chains are alternately formed via the hydrogen-bonds between two adjacent chains. Compound 2 exhibits a layer structure with 4- and 12-MRs formed by ZnO₄ and HPO₃ units, in which two kinds of organic amine molecules both act as countercations to compensate the overall negative electrostatic charge of the anionic network.     

The synthesis of the tripodal phosphine CH3C{CH2P(m-CF3C6H4)2}3 and its rhodium coordination chemistry

The new tripodal phosphine CH₃C{CH₂P(m-CF₃C₆H₄)₂}₃, CF₃PPP, was prepared by reacting CH₃C(CH₂Br)₃ with Li⁺P(m-CF₃C₆H₄)₂⁻, the latter being best obtained by adding Li⁺NⁱPr₂⁻ to PH(m-CF₃C₆H₄)₂. The rhodium complexes [RhCl(CO)(CF₃PPP)], [Rh(LL)(CF₃PPP)](CF₃SO₃) (LL = 2 CO or NBD), [RhX₃(CF₃PPP)], [RhX(MeCN)₃(CF₃PPP)](CF₃SO₃)₂ (X = H and Cl), [RhCl₂(MeCN)(CF₃PPP)](CF₃SO₃) and [Rh(MeCN)₃(CF₃PPP)](CF₃SO₃)₃ were prepared and characterized. The X-ray crystal structure of [Rh(NBD)(CF₃PPP)](CF₃SO₃) is reported. The lower oxygen sensitivity of the CF₃PPP rhodium(I) complexes, relative to the corresponding species with the parent ligand CH₃C(CH₂PPh₂)₃, is attributed to the higher effective nuclear charge on the metal centers caused by the presence of the six CF₃ substituents on the terdentate phosphine. A similar effect may be responsible for the easier hydrolysis of the CF₃PPP-containing, cationic rhodium(III) complexes relative to the corresponding compounds of the parent ligand.     

Uncharged stereoregular nucleic acid analogs: 2. Morpholino nucleoside oligomers with carbamate internucleoside linkages.

A novel oligonucleotide analog has been prepared from ribonucleoside derived morpholine subunits linked by carbamate groups. Oxidative cleavage of the 2',3' vicinal diol of cytidine followed by reductive amination of the resulting dialdehyde afforded the morpholine subunit. Coupling of the subunits are through carbamate moieties and the oligomers were characterized by 1H NMR and FAB MS. Evidence for interaction of the hexamer 19 with p(dG6) was found, but an atypical interaction of 19 with a RNA target was observed.     

小叶章生态系统根际土壤微生物及CO2、CH4、N2O动态

研究了培养 4 5 d的小叶章根际土壤微生物和二氧化碳 ,甲烷及氧化亚氮产生与消耗之间的关系。结果表明好氧微生物与厌氧微生物的空间分布与甲烷 ,二氧化碳及氧化亚氮的产生和氧化有着密切的关系。好氧微生物与甲烷产生呈负相关 ,与二氧化碳和氧化亚氮的产生呈正相关关系。厌氧微生物与甲烷的产生呈正相关 ,与二氧化碳和氧化亚氮的产生呈负相关关系     

Sn-S and Ru-Ru bonds cleavage reactions between [Ph3SnS(CH2)3SSnPh3] and Ru3(CO)12: X-ray crystal structures of [Ph3SnS(CH2)3SSnPh3] and trans-[Ru(CO)4(SnPh3)2]

The organotin complex [Ph₃SnS(CH₂)₃SSnPh₃] (1) was synthesized by PdCl₂ catalyzed reaction between Ph₃SnCl and disodium-1,3-propanedithiolate which in turn was prepared from 1,2-propanedithiol and sodium in refluxing THF. Reaction of 1 with Ru₃(CO)₁₂ in refluxing THF affords the mononuclear complex trans-[Ru(CO)₄(SnPh₃)₂] (2) and the dinuclear complex [Ru₂(CO)₆(μ-κ²-SCH₂CH₂CH₂S)] (3) in 20 and 11% yields, respectively, formed by cleavage of Sn-S bond of the ligand and Ru-Ru bonds of the cluster. Treatment of pymSSnPPh₃ (pymS = pyrimidine-2-thiolate) with Ru₃(CO)₁₂ at 55-60 °C also gives 2 in 38% yield. Both 1 and 2 have been characterized by a combination of spectroscopic data and single crystal X-ray diffraction analysis.     

生物炭与氮肥对旱作春玉米农田CO_2和CH_4排放特征的影响

为了研究生物炭与氮肥对旱作春玉米农田CO_2和CH_4排放通量季节变化、累积排放总量及CO_2+CH_4排放强度的影响,试验设置C_0N_0(不加生物炭,不施氮肥)、C_0N_1(不加生物炭,施氮肥225kg·hm~(-2))和C_1N_1(添加生物炭50t·hm~(-2),施氮肥225kg·hm~(-2))3个处理,采用密闭式静态暗箱-气相色谱法对不同生物炭和氮肥输入旱作春玉米农田CO_2和CH_4排放通量进行连续观测,同时对影响通量变化的0~20cm土层温度和水分因子进行测定。结果表明:(1)试验期内不同处理春玉米农田均表现为CO_2累积通量的源,且CO_2排放通量均呈现一定的峰值变化规律。(2)C_1N_1处理减少了春玉米生长季农田CO_2排放通量和累积排放总量,在试验的2个生长季内农田CO_2平均排放通量和累积排放总量各处理均表现为C_0N_0C_0N_1C_1N_1,且C_1N_1处理降低显著。(3)土壤CO_2排放通量与土壤温度变化呈显著正相关关系,可用指数方程和二次方程较好拟合二者关系,且与10cm土层温度的相关性优于0cm土层温度,但土壤CO_2排放通量与土壤含水量呈负相关关系。(4)试验各处理农田土壤CH_4排放通量在-16.08~-73.96μg·m~(-2)·h~(-1)之间,表现为大气CH_4的净吸收库;C_1N_1处理增加了土壤CH_4排放通量和累积排放总量,但作用效果的显著性受年际环境因子的影响;农田土壤CH_4排放通量与土壤含水量呈显著正相关关系,与土壤温度呈显著负相关关系。研究发现,添加生物炭和施氮减少了旱作农田春玉米生长季CO_2排放通量和累积排放总量,增加了CH_4排放通量和累积排放总量,总体上显著增加了春玉米产量,显著减少农田CO_2+CH_4排放强度。     

Inhibition of reticulocyte iron uptake by NH4Cl and CH3NH2

The aim of this investigation was to test the hypothesis that elevation of intracellular pH would inhibit iron uptake by reticulocytes. The experiments were performed with rabbit reticulocytes and iron bound to rabbit transferrin. Incubation of the cells with NH₄Cl, (NH₄)₂CO₃, CH₃NH₂ and (CH₃)₂NH was used in an attempt to increase intracellular pH. These substances were all found to inhibit iron uptake by reticulocytes. The mechanism of action of NH₄Cl and CH₃NH₂ was investigated in detail. Similar results were found with both reagents. They inhibited iron uptake in a concentration-dependent manner, but produced a small increase in the cellular uptake of transferrin. The onset of action was rapid and the effect was reversible. There was no decrease in the number of transferrin-binding sites per cell and their apparent affinity for transferrin increased slightly, while the efficiency of iron removal from transferrin per binding site diminished greatly. The rate of transferrin release from reticulocytes was unaffected. NH₄Cl did not affect the rate of iron release from transferrin in a cell-free system. Incubation of reticulocytes with 10 mM NH₄Cl or CH₃NH₂ was found to produce an increase in intracellular pH of 0.05—0.15 pH units. The intracellular pH determined by used of the weak acid 5,5-dimethyl-oxazolidine-2,4-dione was significantly higher than that obtained with the weak base (CH₃)₂NH. By transmission electron microscopy it was shown that reticulocytes treated with NH₄Cl or CH₃NH₂ have enlarged intracellular vesicles. The results are considered to support the hypothesis that iron release from transferrin in reticulocytes occurs as a result of protonation of the transferrin within intracellular vesicles. According to this hypothesis, weak bases such as NH₃ and CH₃NH₂ inhibit iron release by neutralizing H⁺ within the vesicles.     

Synthetic and mechanistic studies on ruthenium dicarbonyl complexes containing PhP(CH2CH2CH2PCy2)2 (Cyttp) ligand

A synthetic and mechanistic study is reported on ligand substitution and other reactions of six-coordinate ruthenium(II) carbonyl complexes containing tridentate PhP(CH₂CH₂CH₂PCy₂)₂ (Cyttp). Carbonylation of cis-mer-Ru(OSO₂CF₃)₂(CO)(Cyttp) (1) affords [cis-mer-Ru(OSO₂CF₃)(CO)₂(Cyttp)]O₃SCF₃ (2(O₃SCF₃)) and, on longer reaction times, [cis-mer-Ru(solvent)(CO)₂(Cyttp)](O₃SCF₃)₂ (solvent = acetone, THF, methanol). 2(O₃SCF₃) reacts with each of NaF, LiCl, LiBr, NaI, and LiHBEt₃ to yield [cis-mer-RuX(CO)₂(Cyttp)]⁺ (X = F (3), Cl (4), Br (5), I (6), H (7)), isolated as 3-7(BPh₄). These conversions proceed with high stereospecificity to afford only a single isomer of the product that is assigned a structure in which the Ph group of Cyttp points toward the CO trans to X (anti when X = F, Cl, Br, or I; syn when X = H). Treatment of 2(O₃SCF₃) with NaOMe and CO generates the methoxycarbonyl complex [cis-mer-Ru(CO₂Me)(CO)₂(Cyttp)]⁺ (8), whereas addition of excess n-BuLi to 2(O₃SCF₃) in THF under CO affords mer-Ru(CO)₂(Cyttp) (9). The two ¹³C isotopomers [cis-mer-Ru(OSO₂CF₃)(CO)(¹³CO)(Cyttp)]O₃SCF₃ (2′(O₃SCF₃): ¹³CO trans to P_C; 2″(O₃SCF₃): ¹³CO cis to all P donors) were synthesized by appropriate adaptations of known transformations and used in mechanistic studies of reactions with each of LiHBEt₃, NaOMe/CO, and n-BuLi. Whereas LiHBEt₃ reacts with 2′(O₃SCF₃) and 2″(O₃SCF₃) to replace triflate by hydride without any scrambling of the carbonyl ligands, the corresponding reactions of NaOMe-CO are more complex. The methoxide combines with the CO cis to triflate in 2, and the resultant methoxycarbonyl ligand ends up positioned trans to the incoming CO in 8. A mechanism is proposed for this transformation. Finally, treatment of either 2′(O₃SCF₃) or 2″(O₃SCF₃) with an excess of n-BuLi leads to the formation of the same two ruthenium(0) isomers of mer-Ru(CO)(¹³CO)(Cyttp). These products represent, to our knowledge, the first example of a syn-anti pair of isomers of a five-coordinate metal complex.     

Emission of N2O, N2, CH4, and CO2 from constructed wetlands for wastewater treatment and from riparian buffer zones

We measured nitrous oxide (N₂O), dinitrogen (N₂), methane (CH₄), and carbon dioxide (CO₂) fluxes in horizontal and vertical flow constructed wetlands (CW) and in a riparian alder stand in southern Estonia using the closed chamber method in the period from October 2001 to November 2003. The replicates’ average values of N₂O, N₂, CH₄ and CO₂ fluxes from the riparian gray alder stand varied from −0.4 to 58 μg N₂O-N m⁻² h⁻¹, 0.02–17.4 mg N₂-N m⁻² h⁻¹, 0.1–265 μg CH₄-C m⁻² h⁻¹ and 55–61 mg CO₂-C m⁻² h⁻¹, respectively. In horizontal subsurface flow (HSSF) beds of CWs, the average N₂ emission varied from 0.17 to 130 and from 0.33 to 119 mg N₂-N m⁻² h⁻¹ in the vertical subsurface flow (VSSF) beds. The average N₂O-N emission from the microsites above the inflow pipes of the HSSF CWs was 6.4–31 μg N₂O-N m⁻² h⁻¹, whereas the outflow microsites emitted 2.4–8 μg N₂O-N m⁻² h⁻¹. In VSSF beds, the same value was 35.6–44.7 μg N₂O-N m⁻² h⁻¹. The average CH₄ emission from the inflow and outflow microsites in the HSSF CWs differed significantly, ranging from 640 to 9715 and from 30 to 770 μg CH₄-C m⁻² h⁻¹, respectively. The average CO₂ emission was somewhat higher in VSSF beds (140–291 mg CO₂-C m⁻² h⁻¹) and at the inflow microsites of HSSF beds (61–140 mg CO₂-C m⁻² h⁻¹). The global warming potential (GWP) from N₂O and CH₄ was comparatively high in both types of CWs (4.8 ± 9.8 and 6.8 ± 16.2 t CO₂ eq ha⁻¹ a⁻¹ in the HSSF CW 6.5 ± 13.0 and 5.3 ± 24.7 t CO₂ eq ha⁻¹ a⁻¹ in the hybrid CW, respectively). The GWP of the riparian alder forest from both N₂O and CH₄ was relatively low (0.4 ± 1.0 and 0.1 ± 0.30 t CO₂ eq ha⁻¹ a⁻¹, respectively), whereas the CO₂-C flux was remarkable (3.5 ± 3.7 t ha⁻¹ a⁻¹). The global influence of CWs is not significant. Even if all global domestic wastewater were treated by wetlands, their share of the trace gas emission budget would be less than 1%.     

Crystal structures of MoCl2(O)(O2)(OPMePh2)2 and mixtures of MoCl2(O2)(OPPh3)2 and MoCl2(O)(O2)(OPPh3)2: allylic alcohol isomerization studies using MoCl2(O)(O2)(OPMePh2)2

Adding one equivalent of H₂O₂ to compounds of stoichiometry MoCl₂(O)₂(OPR₃)₂, OPR₃ = OPMePh₂ or OPPh₃, leads to the formation of oxo-peroxo compounds MoCl₂(O)(O₂)(OPR₃)₂. The compound MoCl₂(O)(O₂)(OPMePh₂)₂ crystallized with an unequal disorder, 63%:37%, between the oxo and peroxo ligands, as verified by single-crystal X-ray diffractometry, and can be isolated in reasonable yields. MoCl₂(O)(O₂)(OPPh₃)₂, was not isolated in pure form, co-crystallized with MoCl₂(O)₂(OPPh₃)₂ in two ratios, 18%:82% and 12%:88%, respectively, and did not contain any disorder in the arrangement of the oxo and peroxo groups. These complexes accomplish the isomerization of various allylic alcohols. A mechanism of this reaction has been constructed based on ¹⁸O isotopic studies and involves exchange between the alcohol and metal bonded O atoms.     

Hydrologic gradient and vegetation controls on CH4 and CO2 fluxes in a spring-fed forested wetland

Four different habitats in a spring-fed forested wetland (Clear Springs Wetland, Panola County, Mississippi, USA) varying in hydrologic regime were examined for methane and carbon dioxide fluxes from soils over 15 and 9 months, respectively. There was an increasing gradient of CH₄ flux rates from an unflooded upper-elevation forest site to an occasionally flooded bottomland forest site to a shallow permanently flooded site, and then to a deeper-water permanently flooded site. Depending on the time of year, all sites were sources of methane but only at the upper-elevation forest site, when gravimetric soil moisture content fell below 54%, was atmospheric methane consumed. On average, summer CH₄ emission rates were higher than those in other seasons. A multiple regression model with soil temperature and soil redox potential as independent variables could explain 65% of the variation in CH₄ flux rates. In the flooded zone, variation in CH₄ flux rates was correlated with aboveground plant biomass and stem density of emergent vascular plants, and plant-mediated CH₄ transport depended on plant type. The efflux of CH₄ to plant biomass (Eff:B) ratio was generally lower in Hydrocotyle umbellata compared to Festuca obtusa. Compared to several other freshwater forested wetlands in the southeastern USA, this spring-fed forested wetland ecosystem was a strong source of atmospheric CH₄, likely due to a long hydroperiod and high soil organic matter content. Carbon dioxide fluxes show a reverse spatial pattern than CH₄ fluxes with highest CO₂ emissions in the non-flooded zone at all times of the year, indicating the dominance of aerobic soil respiration. A multiple regression model also revealed a strong dependency of CO₂ fluxes (r ² = 0.73) on soil temperature and soil redox potential. Handling editor: J. M. Melack